CN102527334B - Solid phase extraction column with functionalized multi-walled carbon nanotube substrate, and preparation method thereof - Google Patents
Solid phase extraction column with functionalized multi-walled carbon nanotube substrate, and preparation method thereof Download PDFInfo
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Abstract
The invention specifically relates to a solid phase extraction column with a functionalized multi-walled carbon nanotube substrate, and a preparation method thereof. The substrate of the solid phase extraction column provided by the invention is functionalized multi-walled carbon nanotubes which are prepared from original multi-walled carbon nanotubes by purification, carboxylation, chlorination and functionalization covalence chemical modification. The functionalized multi-walled carbon nanotubes have a packing height of 0.8-1.2cm, and are mainly suitable for reversed-phase extraction of nonpolar to medium polar substances for concentrating and purifying target substances in a sample to be tested. The solid phase extraction column provided by the invention has large adsorption capacity on target substances and high recovery rate (92-103%) of target substances, has the characteristics of low preparation cost, easy availability of material, a simple functionalization process and strong adaptability, and is easy for mass production.
Description
Technical field
The invention belongs to chemical analysis test instrument and equipment field, be specifically related to, the present invention relates to a kind of solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix, the invention still further relates to the preparation method of this extraction column
.
Background technology
SPE (Solid phase extraction, SPE) technology, since the later stage seventies comes out, has obtained significant progress at numerous areas.Replaced gradually traditional liquid-liquid extraction abroad and become the reliable and effective method of sample pre-treatments.The SPE technology is based on a kind of separation, the purification process of liquid chromatogram principle.Its adsorbent is fixing phase, the suction-operated according to solid extracting agent to the liquid phase determinand, and when determinand passes through extractant, wherein the object in sample just is attracted on extractant.Then adopt suitable selective solvent wash-out or pyrolysis absorption, reach the purpose of separation and enrichment target compound.With liquid-liquid extraction, compare, SPE has many good qualities: SPE does not need a large amount of mutual exclusive solvents; President's lactogenesis phenomenon not in processing procedure.It adopts adsorbent (fixedly phase) efficient, high selectivity, can significantly reduce the consumption of solvent, simplifies the processing procedure of sample, and required expense also reduces to some extent simultaneously.In general, the SPE required time is liquid-liquid extraction 1/2, and expense is liquid-liquid extraction 1/5.Its shortcoming is that the rate of recovery and the precision of target compound will be lower than liquid-liquid extraction.
Since Japanese scientist Sumio Iijima in 1991 finds CNT (CNTs), due to electricity, mechanics and the chemical property of CNT uniqueness, become quite concerned in recent years a kind of emerging functional material.CNT has larger specific area and unique surface nature, the conjugated structure system of its tube wall can have with other compound generation strong adsorption effect of conjugated structure, make it to the organic and inorganic pollution in the environment matrix, all there is certain suction-operated and larger adsorption capacity, thereby CNT have unique advantage as a kind of solid extracting agent.The research discovery, the adsorption capacity of multi-walled carbon nano-tubes (MWCNTs) is better than C
18, silica and active carbon.After the absorption of CNT, wash-out, carry out again the analyses such as mass spectrum, gas-chromatography, high performance liquid chromatography, Capillary Electrophoresis, atomic absorption spectrum, simplify the preprocessing process of sample, can be successfully applied to the detection of different pharmaceutical and aromatic hydrocarbon and linear paraffin compound.
At present, take CNT on adsorbent carries out research that the Solid phase extraction separation enrichment mainly concentrates on organic compound and metal ion.Utilize recently the research of carbon nanotube adsorption large biological molecule also to make some progress, the CNT of carboxylated can be used for separating alkaline protein, thereby likely this novel, efficient adsorbent is applied to extract the large biological molecule in biological sample.In addition, CNT also has good bio-compatibility, has the ability that retains the large biological molecule activity be adsorbed, therefore usings its adsorbent as the SPE large biological molecule to have a wide range of applications.The multi-walled carbon nano-tubes of functionalization can be realized the specific absorption to target substance, and its adsorbance is larger than common MWCNTs SPE post, has improved the rate of recovery of target substance.Therefore can prepare for different target substances the multi-walled carbon nano-tubes of the functionalization of difference in functionality.See commercial f-MWCNTs SPE post but seldom have on market, f-MWCNTs SPE post is to load by hand by the experimenter mostly, and difficulty has certain standard.
CNT is a kind of high molecular inorganic material, and between tube and tube, absorption affinity is stronger, so the water insoluble and organic solvent of CNT and bunchy be difficult to disperse, and this is the restriction CNT in the application study of every field main cause widely only.
Summary of the invention
The object of the invention is to provide a kind of solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix, it will be as a kind of novel sample pre-treatments material, the nonpolar material to middle polarity of reversed phase extraction, for the target substance of enrichment, purification water sample, food or cosmetics.
Another object of the present invention is to provide the preparation method of the solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix.
The object of the present invention is achieved like this: a kind of solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix, the multi-walled carbon nano-tubes that the matrix that it is characterized in that described solid-phase extraction column is functionalization, the multi-walled carbon nano-tubes of this functionalization (f-MWCNTs) is that the step covalent chemical such as, carboxylated purified by original multi-walled carbon nano-tubes, chloride, functionalization are modified gained, and covalent chemical is modified and carried out according to the following steps:
(1) purifying: 10～20 h that the MWCNTs of certain mass is refluxed in 35% hydrochloric acid under 80 ℃～100 ℃, under the washing of suction filtration, deionized water, 100 ℃, dry 3 h obtain the MWCNTs of purifying;
(2) carboxylated: in the mixed liquid that the MWCNTs of purifying is the concentrated sulfuric acid: red fuming nitric acid (RFNA)=3:1 in volume ratio, 80～100 ℃ of 5 h that reflux, the dark solution after having reacted is diluted by deionized water, after stratification, removes the acid clear liquid in upper strata; The MWCNTs-COOH got off with precipitation and separation with the filter membrane decompress filter, and be washed till neutrality by deionized water; Filter to obtain product 50～80 ℃ of drying 3 h in vacuum drying chamber;
(3) chloride: join after dried MWCNTs-COOH porphyrize new steaming SOC1 is housed
2, DMF single necked round bottom flask in, 70 ℃～150 ℃ lower magnetic force stirring and refluxing 20～30 h, be converted into the chloride multi-walled carbon nano-tubes with the MWCNTs-COOH carboxylated; Reacted rear distillation or centrifugally removed unnecessary SOC1
2and DMF;
(4) functionalization: by after (3) products therefrom evaporate to dryness, add ethylaminobenzoate magnetic agitation in oil bath device 20 h～50 h that reflux; Cool to room temperature, use the filter membrane decompress filter, and use absolute ethanol washing, and product is dried overnight in 50～80 ℃ of vacuum drying chambers, obtains final functionalization multi-walled carbon nano-tubes.
The solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix of the present invention, the granularity of its multi-walled carbon nano-tubes is 5～50 μ m, and solid-phase extraction column blank pipe volume is 1～6 mL, and loading is highly 0.6～1.2 cm, and the blank pipe material is polyolefin.
The solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix of the present invention, its preparation method step in the following order carries out:
(1) the polyethylene sieve plate of a micropore is put into to the bottom of solid-phase extraction column blank pipe;
(2) a certain amount of functionalization multi-walled carbon nano-tubes is mixed with a certain amount of diatomite, dry packing enters in post;
(3) put into another polyethylene sieve plate at functionalization multi-walled carbon nano-tubes and diatomite mixture upper end again;
(4) the compression filler makes to load the post height and remains on 0.6～1.2 cm, is prepared into solid phase extraction column.
Described functionalization multi-walled carbon nano-tubes is packed into before post needs to remove fully the moisture of absorption, can be under 100 ℃ in drying box baking 3 h.
The solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix of the present invention needs to be purified and the pretreatment such as activation with deionized water, ethyl acetate, acetone or methyl alcohol before use.
F-MWCNTs SPE post of the present invention is loaded principle: SPE column jecket and sieve plate are all with standardized production, column jecket height and plate thickness are fixed value, solid-phase extraction column of the present invention is actually the volume of regulating the institute receiving fluids by the adjustable column diameter, so we select the functionalization multi-walled carbon nano-tubes of different amounts according to different diameters, having loaded by control in the solid-phase extraction column of functionalization multi-walled carbon nano-tubes that f-MWCNTs loads is highly 0.8～1.2 cm, thereby guarantees that post imitates.
From present solid-phase extraction column, adopt homogenate high pressure loading method different, f-MWCNTs SPE post adopts the density degree of loading f-MWCNTs filler in the SPE post that highly the control method guarantees to have loaded, coutroi velocity then.Concrete process for adding a certain amount of f-MWCNTs and diatomite mixed fillers in solid-phase extraction column, slowly sieve plate is depressed, in the process of depressing constantly the concussion pillar to guarantee in pillar that f-MWCNTs loads density up and down consistent, making packed height is 0.8～1.2 cm.
The present invention is using the functionalization multi-walled carbon nano-tubes as main stuffing, diatomite is as carrier, be made into solid-phase extraction column, the f-MWCNTs SPE post of having loaded is a kind of polarity solid phase extraction column, its performance is compared with common CNT SPE post, because f-MWCNTs SPE post has specific functional group, it is better than common CNT SPE post to the absorption property of target substance, for the rate of recovery that improves target substance, has played certain effect.Because f-MWCNTs is reversible to the absorption of material, so can be as using C
18the SPE post is the same, by adjusting the polarity of eluting solvent, target substance is eluted.The using method of the two is very close, before using, by methyl alcohol or deionized water, activate, loading solution is also water, by regulating the vacuum control flow velocity, make solution pass through the SPE post with suitable flow velocity, material is retained on the SPE post, can vacuum drains and dewaters, organic solvent drip washing and the wash-out of suitable polarity for material.It mainly is suitable for the nonpolar material to middle polarity of reversed phase extraction, for enrichment, purification sample target substance.
The invention has the beneficial effects as follows:
(1) solid-phase extraction column inevitably to be activated in use, the operation of purification, wash-out, therefore need to use different solvents.When being added solvent, require to change when liquid level drops to sieve plate to add different solvents, Ruo Jia get too late, can make the dry bubble that produces in filler, affects the stability of result; Ruo Jia get Tai early, can make the original solution of solution on sieve plate added mix, produce one we do not wish to exist and can't expect the new eluent of polarity, the reliability of experimental result is reduced.But f-MWCNTs SPE post can be avoided this problem, because the multi-walled carbon nano-tubes filler more general to the adsorptivity of multi-solvents is strong, the wetability of liquid level is kept to the long period, can make the operator have the sufficient time to change different solvents.
(2) f-MWCNTs SPE post is compared with traditional reverse phase solid phase extraction post MWCNTs SPE post, and this extraction column adsorption capacity is large, and can specific suction-operated be arranged to predetermined substance, can improve the rate of recovery to target substance.The multi-walled carbon nano-tubes cost is low, and material is easy to get, and commercial SPE void column preparation used is simple, is easy to batch production, cost, and the functionalization experimental program is flexible and changeable, and the scope of application of f-MWCNTs SPE post is increased.
(3) due to f-MWCNTs SPE post preparation technology's restriction, larger 5～100 μ m of packing material size length range that produce, so generally load on effect usually very tight, by adding a certain amount of diatomite, not only make the MWCNTs SPE post that velocity ratio is general fast, and be conducive to target substance and fully act on f-MWCNTs, thereby improve concentration effect in f-MWCNTs SPE post.
(4) during the setting up of experimental technique, can make part and revise with reference to the use data of existing nonpolar SPE post, can set up as soon as possible system.
The accompanying drawing explanation
Fig. 1 is the synthetic route chart of functionalization multi-walled carbon nano-tubes (f-MWCNTs).
Fig. 2 purifies the parabens anticorrisive agent (mark-on) in cosmetics with the enrichment of f-MWCNTs SPE post.
Peak information: (1) methyl hydroxybenzoate; (2) ethylparaben; (3) nipalgin isopropyl ester; (4) propylben; (5) nipalgin isopropyl ester; (6) butyl hydroxybenzoate.
Fig. 3 purifies the parabens anticorrisive agent (not mark-on) in cosmetics with the enrichment of f-MWCNTs SPE post.
Peak information: (3) nipalgin isopropyl ester.
The specific embodiment
Below in conjunction with example, the present invention is described in further detail.
A. the preparation of extraction column
1, void column material and specification
Existing solid phase extraction column void column specification does not wait to 10 g/60mL from 0.05 g/1mL.The void column material is polypropylene, and pillar respectively has the polyethylene sieve plate in 20 μ m apertures up and down.Above-mentioned void column all can be used in the present invention, and in experimental example below, the present invention adopts 0.25～0.30 g/3mL.
2, the granularity of MWCNTs (length)
The filler granularity of solid-phase extraction column is generally at 5～50 μ m, and the aperture of polyethylene sieve plate is 20 μ m, in order not make filler flow out from sieve plate, we select the MWCNTs that length is 5～50 μ m to carry out functional modification as modified feedstock, using modification products therefrom f-MWCNTs as the SPE matrix fill.
3, the selection of amount of fill and filling height
The flow velocity of SPE post is with amount of fill and load highly relevant.Amount of fill is more, loads highly highlyer, and flow velocity is slower, and experimental period is also corresponding longer.According to this principle, for f-MWCNTs SPE post, on amount of fill, we select to adopt the specification of 0.050～0.150 g/3 mL; Loading on height, we adopt and load is highly that 0.8～1.2 cm(is containing diatomite).
Load 3 mL solid-phase extraction columns by aforementioned A step method, load height 0.8～1.2 cm, amount of fill is 0.08～0.15 g/3 mL.Use the parabens material (mark-on reclaims and actual sample detects) in above-mentioned solid phase extraction column extraction cosmetics.
F-MWCNTs SPE post needs before using with deionized water, ethyl acetate, acetone or methyl alcohol pretreatment.
Detailed process is as follows: take 2 parts of 1 g cosmetic samples, sample 1 adds 6 kinds of parabens anticorrisive agent standard items (6 kinds of anticorrisive agent additions are 2.5 μ g), does not add the standard material in sample 2.Sample 1,2 is placed in 2 different centrifuge tubes, is settled to 5 mL with mobile phase respectively, ultrasonic extraction 30 min, after extract suitably dilutes, with 0.5 μ m membrane filtration, sample 1,2 filtrates are for the solid-phase extraction column loading.After two f-MWCNTs SPE posts have activated, make above-mentioned 2 kinds of filtrates respectively by f-MWCNTs SPE post, coutroi velocity is 3～5 mL/min.After filtrate is all by the SPE post, with 10 mL deionized water drip washing, moisture is removed in each self-pressurization.Then the dry 10min that places starts wash-out and collects eluent with 3 mL methyl alcohol respectively, and pressurization is drained, then adds 2 mL methyl alcohol carry out the secondary wash-out and collect eluent, and twice eluent is collected together.Eluent dries up with condensed nitrogen, with the mobile phase vibration, dissolves, and is settled to 200 μ L, carries out the HPLC analysis, and the HLPC chromatogram is shown in Fig. 2 and Fig. 3.
Fig. 2 purifies the parabens anticorrisive agent (mark-on) in cosmetics with the enrichment of f-MWCNTs SPE post.
Peak information: (1) methyl hydroxybenzoate; (2) ethylparaben; (3) nipalgin isopropyl ester; (4) propylben; (5) nipalgin isopropyl ester; (6) butyl hydroxybenzoate.
Fig. 3 purifies the parabens anticorrisive agent (not mark-on) in cosmetics with the enrichment of f-MWCNTs SPE post.
Peak information: (3) nipalgin isopropyl ester.
F-MWCNTs SPE post is respond well for 6 kinds of parabens anticorrisive agent enriching pollutants in cosmetics as seen from the figure, and the recovery of standard addition of all types of target thing reaches 92-103%, can be well for actual cosmetics sample detection.Wherein the content of nipalgin isopropyl ester in cosmetics can be detected be 0.52 μ g/g to Fig. 2.
Embodiment 2
Load 6 mL solid-phase extraction columns by aforementioned A step method, load height 0.8～1.2 cm, amount of fill is 0.15～0.30 g/6 mL.Use the enrichment of above-mentioned solid phase extraction column to purify the polycyclic aromatic hydrocarbon in water sample.
Before being used, f-MWCNTs SPE post uses deionized water, ethyl acetate, acetone or methyl alcohol pretreatment.
Detailed process is as follows: gather respectively seawater and river sample, sample is centrifugal respectively, gets supernatant 200 mL, and with 0.5 μ m membrane filtration, filtrate is transferred in corresponding 200 mL volumetric flasks.Get the f-MWCNTs SPE post of two 6 mL that loaded, by deionized water, ethyl acetate, acetone or methyl alcohol activation process, make above-mentioned two kinds of filtrates respectively by f-MWCNTs SPE post, under vavuum pump, coutroi velocity is 3～5 mL/min.After filtrate is all by the SPE post, with 10 mL deionized water drip washing, moisture is removed in each self-pressurization.Then the dry 10min that places starts wash-out and collects eluent with 2 mL methyl alcohol respectively, and pressurization is drained, then adds 1 mL methyl alcohol carry out the secondary wash-out and collect eluent, and twice eluent is collected together.Eluent dries up with condensed nitrogen.With 0.5 mL n-hexane (analyzing pure through heavily steaming) dissolved residue, sample introduction 2 μ L carry out the GC analysis.In detection river sample, eight kinds of polycyclic aromatic hydrocarbon contents are between 3.5～10.2 μ g/L; Do not detect polycyclic aromatic hydrocarbon in seawater sample.The recovery of standard addition of actual water sample is between 89%～95%.
The aforementioned A step method of experimental example 3 use is loaded 6 mL solid-phase extraction columns, loads height 0.8～1.2 cm, and amount of fill is 0.15～0.30 g/6 mL.Use the Detection of neomycin residues in above-mentioned solid phase extraction column enrich milk sample.
Before being used, f-MWCNTs SPE post uses deionized water, ethyl acetate, acetone or methyl alcohol pretreatment.
Detailed process is as follows: measure 10 mL plain chocolates in 15 mL polypropylene plastics centrifuge tubes, add certain volume 10 μ g/mL neomycin titers, vibration evenly, obtains the mark-on milk sample containing the finite concentration neomycin.Toward wherein adding 1 mL 0.2 g/mL trichloroacetic acid solution, 1 min that vibrates, centrifugal 30 min under 25 ℃ of 6000 g condition.The careful upper strata 5 mL clarified solutions of drawing are for the solid-phase extraction column loading.After f-MWCNTs SPE post has activated, make supernatant pass through f-MWCNTs SPE post, coutroi velocity is 3～5 mL/min.After supernatant liquid is all by the SPE post, with 10 mL deionized water drip washing, moisture is drained in pressurization.Pillar is dry to be placed 5 minutes.Finally with 1 mL 0.3 mol/L HClO
4solution divides the secondary wash-out and collects eluent, and eluent dries up with condensed nitrogen, with the mobile phase vibration, dissolves, and is settled to 200 μ L, carries out the HPLC analysis.In milk sample, the mark-on of neomycin is recovered between 93%～101%.
Claims (3)
1. the solid-phase extraction column of a functionalization multi-wall carbon nano-tube matrix, the multi-walled carbon nano-tubes that the matrix that it is characterized in that described solid-phase extraction column is functionalization, the multi-walled carbon nano-tubes f-MWCNTs of this functionalization is that, carboxylated purified by original multi-walled carbon nano-tubes, chloride, functionalization step covalent chemical are modified gained, and covalent chemical is modified and carried out according to the following steps:
(1) purifying: 10～20h that the MWCNTs of certain mass is refluxed in 35% hydrochloric acid under 80 ℃～100 ℃, under the washing of suction filtration, deionized water, 100 ℃, dry 3h obtains the MWCNTs of purifying;
(2) carboxylated: in the mixed liquid that the MWCNTs of purifying is the concentrated sulfuric acid: red fuming nitric acid (RFNA)=3:1 in volume ratio, 80～100 ℃ of backflow 5h, the dark solution after having reacted is diluted by deionized water, after stratification, removes the acid clear liquid in upper strata; The MWCNTs-COOH got off with precipitation and separation with the filter membrane decompress filter, and be washed till neutrality by deionized water; Filter to obtain product 50～80 ℃ of dry 3h in vacuum drying chamber;
(3) chloride: join after dried MWCNTs-COOH porphyrize new steaming SOC1 is housed
2, DMF single necked round bottom flask in, 70 ℃～150 ℃ lower magnetic force stirring and refluxing 20～30h, be converted into the chloride multi-walled carbon nano-tubes with the MWCNTs-COOH carboxylated; Reacted rear distillation or centrifugally removed unnecessary SOC1
2and DMF;
(4) functionalization: by after (3) products therefrom evaporate to dryness, add ethylaminobenzoate magnetic agitation backflow 20h～50h in oil bath device; Cool to room temperature, use the filter membrane decompress filter, and use absolute ethanol washing, and product is dried overnight in 50～80 ℃ of vacuum drying chambers, obtains final functionalization multi-walled carbon nano-tubes.
2. the solid-phase extraction column of functionalization multi-wall carbon nano-tube matrix according to claim 1, the filler granularity of described functionalization multi-walled carbon nano-tubes is 5～50 μ m, solid-phase extraction column blank pipe volume is 1～6mL, and loading is highly 0.6～1.2cm, and the blank pipe material is polyolefin.
3. according to the solid-phase extraction column of the functionalization multi-wall carbon nano-tube matrix of claim 1 or 2, its preparation method step in the following order carries out:
(1) the polyethylene sieve plate of a micropore is put into to the bottom of solid-phase extraction column blank pipe;
(2) a certain amount of functionalization multi-walled carbon nano-tubes is mixed with a certain amount of diatomite, dry packing enters in post;
(3) put into another polyethylene sieve plate at functionalization multi-walled carbon nano-tubes and diatomite mixture upper end again;
(4) the compression filler makes to load the post height and remains on 0.6～1.2cm, is prepared into solid-phase extraction column.
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| CN106617060A (en) * | 2016-12-27 | 2017-05-10 | 云南中烟工业有限责任公司 | Fructus phyllanthi polyphenols enriching and purifying method |
| CN106770797B (en) * | 2017-01-25 | 2019-03-15 | 山东省分析测试中心 | The analysis method of perfluor acids pollutant in a kind of water based on carboxylated nano carbon microsphere material |
| CN108159734A (en) * | 2018-01-12 | 2018-06-15 | 浙江省食品药品检验研究院 | A kind of amino multi-walled carbon nano-tube solid-phase extraction column and preparation method thereof |
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| EP0913508A2 (en) * | 1997-10-30 | 1999-05-06 | Canon Kabushiki Kaisha | Carbon nanotube device, manufacturing method of carbon nanotube device, and electron emitting device |
| WO2004106223A1 (en) * | 2003-05-30 | 2004-12-09 | Fuji Xerox Co., Ltd. | Carbon nanotube device, process for producing the same and carbon nanotube transcriptional body |
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| EP0913508A2 (en) * | 1997-10-30 | 1999-05-06 | Canon Kabushiki Kaisha | Carbon nanotube device, manufacturing method of carbon nanotube device, and electron emitting device |
| US7048901B2 (en) * | 2001-03-16 | 2006-05-23 | Fuji Xerox Co., Ltd. | Electrical connection structure, production method thereof, and electric wiring method |
| WO2004106223A1 (en) * | 2003-05-30 | 2004-12-09 | Fuji Xerox Co., Ltd. | Carbon nanotube device, process for producing the same and carbon nanotube transcriptional body |
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